Alkylation process



Feb. 27, 1945., M HEMPHlLL 2,370,164

ALKYLATION PROCESS I Filed June 17, 1941 lnvemor: Sam: M. HemphiH By his Afrorney-MKM! Patented Feb. 27, 1945 UNITED i STATES PATENT- OFFICE ALKYLATION PROCESS lsaac M. Hemphlll, Wilmington, Calit, assignor to Shell Development Company, San Francisco, CaliL, a corporation of Delaware Application June 17, ion, Serial No. 398,423

8 Claims.

more, economical alkylation process which is easier to operate. Another object is the provision of an alkylation method in which more constant plant operating conditions may be maintained. A further object is to eliminate the loss I can be reestablished.

provides a method of operation whereby the adof plant capacity heretofore involved in batch replacement of catalyst without. sacrifice of catalyst life or product quality. It is also an ob- .iect of the invention to provide a continuous method of operating a plurality of alkylation units with reduced supervision expense.

The alkylation of isoparafflns with oleilnes has been widely adopted by the petroleum industry for the production of superior motor fuels. Particularly advantageous methods of carrying out the reaction are described, for example, in United States patents, 2,211,747, 2,232,674 and 2,238,802. In all of these methods of operation the catalyst loses its activity during use and must be replaced by fresh or reactivated'catalyst. This decrease in catalyst activity is associated with a decrease in the concentration of the catalyst and there are indications that the quality of the alkylate drops with the concentration of the catalyst. If the catalyst is continuously replaced, as by continuously feeding in fresh catalyst and withdrawing a corresponding volume of used catalyst from the system, the process must be carried out with catalyst which gives the poorest quality product in order to avoid excessive catalyst consumption. This undesirable condition has been avoided in the past by batch replacement of the catalyst.v By this procedure the bulk of the product may be obtained with catalyst which has not dropped in concentration to a point where the decrease in product quality becomes noticeable. However, such batch replacement involves substantial loss or plant capacity during the periods in which entire plant and require repeated readjustments to be made before uniform operating conditions The present invention vantages of both batch and continuous methods of catalyst replacement may be obtained without the disadvantages of either.

According to the invention, isoparamns and naphthenes having a tertiary carbonatom are alkylated in a plurality of reaction stages, to each of which is fed the hydrocarbon to be alkylated and an alkylating agent. In each stage the reactants are emulsified with a liquid alkylation catalyst under suitable alkylation conditions, the most important of which is that a large excess of the hydrocarbon being alkylated is maintained relative to the alkylating agent used. From each reaction stage reacted emulsion is withdrawn to a separator in which product containing hydrocarbon is separated fromlthe catalyst and removed from the system for recovery of the alkylate while separated acid is returned to the corresponding reaction stage. F1'8Sh catalyst is fed to one reaction stage only, the catalyst for the succeeding stages being supplied in the form of emulsified reaction mixture from a previous reaction stage and spent catalyst is withdrawn fromv the last reaction stage.- drawing shows, diagrannnatically, a preferred assemblage of apparatus for carrying out the process in three stages. The process is equally advantageous when two, four or more stages are used. A

In the drawing, line I represents a supply line for the saturated tertiary carbon atom containing aliphatic hydrocarbon to be alkylated,

for example, an isoparaflin such as isobutane or isopentane, and line 2 is the supply line for the olefine or the like to be used as alkylating agent. These reactants are blended in tank 3, preferably in proportions corresponding to a molecular excess of isoparaflln to olefine, advantageously 3 to 10 or more mols of saturated aliphatic tertiary hydrocarbon per mol of alkylating agent. It is feasible to omit blending tank 3 and feed the reactants directly to the reaction circuit, particularly when using alkvlating agents which are less reactive than olefines, for example, alkyl halides. From tank 3 the reactants are fed The attached those used in the first reaction unit, inwhich second reactor. Reacted emulsion is withdrawn content to the feed. to the second unit is conat a uniform regulated rate by line 4 to line 5. under the same conditions. In addition the dif- In line 5 the feed is mixed with an emulsion of ilculties .encountered due to freezing of the reacted hydrocarbon and catalyst which is concatalyst just after charging a fresh batch to the tinuously circulated by pump 6 through a closed reactor when using 98% sulfuric acid, for circuit comprising line 1, cooler 8, line 9, time 5 example, are avoided since the acid in the units tank In and line 5. From the circulating stream will always be of lower titratable acidity than of reaction mixture, emulsion is continuously the fresh acid. Furthermore, variation of the withdrawn by line H. A part of this withdrawn op rati temperature in co a c wit va iaemulsion is conducted by line l2 to a separator l3 tions in the cataly concentration is n er in which the mixture is allowed to stratify: The 10 u ssa y s n a un t may be p at d at hydrocarbon layer containing alkylation products a substantially constant catalyst concentration. and excess is p r mn i r m v d by i I whi In commercial scale operations of the process the separated catalyst is returned via line It to it has been found t n y that t aterase of the reaction; The remainder of the withdrawn the entire lirofiluet r a Of t reactors i fully that obtained by prior methemulsion is conducted by line ii to the second 5 equal Superior to reaction unit, to which it is preferably fed to the ode of operation but o t t ri in y t e suction side of circulating pump ll. This pump quality of the .alky forms part of a closed circuit analogous to that which catalyst of the lowest concentration is used of the consisting of line I cooler is substantially the Same as Of the alkylate line 20, time tank. and return conduit 22. The Imm first reactor in which mhch higher reactants fed to this unitmay be the same as catalyst is maintained- The process of the invention is of particular advantage in the alkylation of isoparaflins and alkyl naphthenes with oleflnes such, for example, as propylene, the butylenes', amylenes, cyclopen case they may be supplied, for example, via lines 23 and 24. Where one or both of the reactants used in the second unit are different from those employed m the fir t they may be supplied by tene, cyclohexene and higher oleflnes as, for inlines 25 and 2a to tank 21 from which the blended Stance in G end Wmt cracked mixture may be fed by lines 2: and 24 to the "firmed end the like Instead olefines, themselves, polymers thereof or esters, from the circulating stream of reaction mixture so either immune mslmdln! m by line A part equivalent m hydrocarbbn such olefines or polymers maybeused. Inorganic or organic esters of primary alcohols such as ducted via line to separator 3|, from which methyl ethyl} pmpyl' butyl' isobutyl e like alcohols may be employed as alkylating agents product contalnmg hydrocarbon is removed by instead of the secondary and tertiary when can late from the last reactor in lin 32 85 e while separated catalystis returned to the responding to the 1eflne8 The process is also 7 reaction circuit by line 33. The remaining emul-.

sion which preferably is of an amount sufllcient advantageous when or alcoholga 3:3 to supply the catalyst requirements of the third ashthe fl t: mcl i y like: 1 reaction unit is fed by line 34 to the circuit conw en m gmagen g i g sisting of conduits 35, 36 and I1, circulating pump g 0 m a s a, cooler 29 and time tank to. The hydrocarbon e feed to this circuit may be introduced via lines muted almatmgagen as 2:, 4| and 42 if it is the same asthat used in the mm m l made empmyed first unit or'by lines 28 a and u u it is and the expresslonalkylating agent will therethe same as that used second but 45 forebe understoodas referring generically toany different from the feed to the first unit Feed compound capable of substituting an alkyl group, lines a and l w blending tank 5 may used which may or may not contain one or more subwhen the feeds to all of the un'ts are different 2%: iz gs-g 1x535, tf fffig the blended feed then being conducted to the reacfi a 2: f wide mpg in tion circuit by lines 46 and 42. From the third m to the alkylating agents hi h may be used, unit only so much emulsion is preferably withb t lso with respect to the tertiary aliphatdrawn via line 41 as is required for recovery of the 1 carbon t m-containing compounds which elkylatien p o of this unit The Be wlthmay be alkylated thereby and the alkylation acid drawn emulsion is conducted to separator 48 from catalysts which y be used. Thus, for example. which the product-containing phase is removed t ad of isobutane, isopentane, isohexane, by line 49 while acid phase is withdrawn by line 2, 2, 5-t i myl hexane, methyl cyclopentane, M. A part Of the withdrawn catalyst is returned methyl cyclohexane, ortho dimethyl cyclohexane ly line ii to the third reaction unit while the reand the like and suitable substitution products.

Ina-hide! is removed from the syjtem by line so as 1-chloro-4-methyl-pentane,etc., may be alk l- The catalyst thus removed is r placed by fresh ated by the process of the invention. In place acid introduced into the first reactionunit by line of sulfuric acid, halo-sulfonic acids or phosphoric I acid or mixtures of sulfuric or phosphoric acids BY th n w method or op r n he p a m with boron fluoride and/ or a hydrogen halide or be run continuously under the same constant 05 organic complexes of aluminum chloride or mixconditions. The operations are smoother at all tures of aluminum chloride with antimony.

stages. Even the distilling columns, not shown chloride or the like such as are described in in the drawing, for recovering excessisoparaflln copending application, Serial No. 380,892, filed or alkyl naphthene to be recycled to the reaction February '27, 1941, or other suitable agents may from the hydrocarbon withdrawn through lines be used as the alkylation catalyst.

14, 82 and 49, operate more uniformly as a result The particular reaction conditions which it will of the elimination of fluctuations resulting from be most advantageous to maintain irregular reactor operation. The yield and qualreaction stages will depend upon the particular ity of the'alkylation products are also more uniisoparamn or naphtbene being alkylated and the A form because the reactors operate permanently II alhlating' agent and alkvlation catalyst chosen.

Is'oparaffln to olefine feed ratio 3:1 to 12:1

Isoparafiln concentration in the feed 50% to 90% Fresh H2804 catalyst concentration 96% to 100% Reaction temperature C. to 30 C. Acid to hydrocarbon volume ratio in reactor 0.6 to 1.5

Volumes of recycled hydrocarbon per .volume of feed 15 to 100 Olefine feed rate (volumes of liquid per volume of catalyst per hour)- 0.06 to 0.30 Average residence time of hydrocarbon in reactor"; to 60 min. Pressure Sufficient to maintain the reactants substantially in the liquid phase It is not necessary, even when using the same reactants in all stages, to use the same conditions in each stage. As a general rule, it is advantageous when carrying out different alkylations in difie'rent reaction stages to feed the more readily alkylatable reactants to the later stage or stages of the system. Thus, for example, if isobutane and isopentane are to be separately reacted it is preferable to feed the latter to the last reaction stage. Similarly, where 'butylenes and amylenes are being used as alkylating agents it is advantageous to use the former in the early stage or stages and feed the amylenes to the later reaction stage or stages.

It is preferable to carry out the process so that the drop in catalyst concentration is approximately the same in each of the reaction stages. Thus, for example, in alkylating isobutane with secondary butylenes in the presence of sulfuric acid in three reaction stages, excellent results have been obtained by feeding fresh ae% acid to the first stage in which an acid concentration of about 95% ismaintained, maintaining the acid concentration in the second stage at about 92% and discharging acid from the final stage at about 89% concentration. In this type ofv operation the plant capacity has been increased 12% and the octane number and yield of light alkylate as well as the acid life have been increased compared with'similar operations carried out in the same plant using batch replacement of acid. As a general rule it is advantageous, when using sulfuric acid as the catalyst, to maintain an acid concentration of about 92% to 97% in one of the reaction stages while maintaining a lower concentration within the range of about 95% to 88% in a subsequent reaction stage by feeding thereto acid from the first said stage.

The transfer of emulsion from one stage to another has been emphasized as the preferred tion. It,will be seen that the invention offers advantages over countercurrent or concurrent multi-stage method of carrying out the alkylation of isoparamns and the like. In particular, it avoids excessive contact of alkylate with catalyst such as may promote undesirable side reactions.- I

The invention is capable of considerable modification. For example, two or more reactors in parallel'may be used in place of any one or more of the reaction stages through which the acid flows in series. Also, the catalyst supplied to the later reaction stages from an earlier stage or stages may be supplemented by fresh catalyst, although this procedure is generally less desirable because it adds to the difficulties of control. Still other changes may be made without departing from the invention.

, I claim as my invention:

1. A process of alkylating a saturated aliphatic hydrocarbon having a tertiary carbon atom by reaction with an alkylating agent in the presence of an alkylation catalyst in the liquid phase in a plurality of reaction stages through which said catalyst passes in series, fresh catalyst being supplied only to theflrst of said reaction stages while spent catalyst is withdrawn only from the last of said stages, which comprises feeding the fresh saturated aliphatic hydrocarbon having a tertiary carbon atom which is to be alkylated and fresh alkylating agent to each of said reaction stages, intimately contacting said reactants therein with the alkylation catalyst under alkylating conditions to form a reacted emulsion, withdrawing reacted emulsion from each reaction stage, separating a part of said withdrawn emulsion to recover product-containing hydrocarbon from catalyst which is returned to the same reaction stage and feeding another part of said withdrawn emulsion from each reaction stage, except the last, to the next succeeding reaction stage of the series to supply catalyst thereto.

2. A process of alkylating a saturated aliphatic hydrocarbonhaving a, tertiary carbon atom by reaction with an olefin in the presence of an alkylation catalyst in the liquid phase in at least two reaction stages through which said catalyst passes in series, fresh catalyst being supplied only to the first of said reaction stages while spent catalyst is withdrawn only from the last (if said stages, which comprises feeding the fresh saturated aliphatic hydrocarbon having a tertiary carbon atom which is to be alkylated and said olefin to each of said reaction'stages, intimately mixing said reactants therein under alkylating conditions to form a reacted emulsion, withdrawing said reacted emulsion, separating a part of said withdrawn emulsion to recover product-containing hydrocarbon therefrom, feeding another part of said withdrawn emulsion from each reaction stage, except the last, in suflicient amount to the next succeeding reaction stage of the series to maintain a substantially constant ratio of catalyst to hydrocarbon therein.

3. A process of alkylatingan isoparaflin by reaction with an alkylating agent in the presence of an alkylation catalyst inthe liquid phase, in a plurality of reaction stages through which said catalyst passes in series, fresh catalyst being supplied only to the first of said reaction stages while used catalyst removed from the systemis taken only from the last of said stages, which comprises feeding fresh isoparafiln and fresh alkylating agent to each of said reaction stages, intimately contacting said reactants therein with the alkylation catalyst under alkylating condi- *1 tions to form' areacted emulsion. withdrawing reacted emulsion. from each reaction stage. separating a part of said withdrawn emulsion to recover product-containing hydrocarbon from catalyst and feeding another part of said unseparated withdrawn emulsion from each reaction stage, except the last, to the next succeeding reaction stage of the series to supply catalyst thereto.

4. A process of alkylating an isoparaifin by reaction with an olefin in the presence of an acid alkylation catalyst in the liquid phase in a plurality of reaction stages through which said catalyst passes in series, fresh catalyst acid being supplied only to the first of said reaction stages while used catalyst is withdrawn from the system from the last of said stages, which comprises feeding fresh isoparafiin and olefin to each of said reaction stages, continuously withdrawing reacted emulsion from each reaction stage, feed ing a major portion of the withdrawn emulsion to a separator in which product-containing hydrocarbon is separated from catalyst acid and feeding the remaining minor portion of unseparated emulsion from each reaction stage, except the last, to the next succeeding reaction stage of the series.

5. A process of alkylating isobutane by reaction with a normally gaseous olefin of at least three carbon atoms per molecule in the presence of concentrated sulfuric acid in a plurality of reaction stages through which the sulfuric acid passes in series, fresh sulfuric acid being supplied only to the first of said reaction stages while used sulfuric acid catalyst phase is removed from the system only as catalyst withdrawn from the last of said reaction stages, which comprises feeding fresh isobutane and olefin to each of said reaction stages, continuously withdrawing reacted emulsion from each reaction stage, feeding a portion of the withdrawn emulsion to a separator in which product-containing hydrocarbon is separated from sulfuric acid catalyst and passing another portion of the unseparated withdrawn emulsion from each reaction stage, except the last, to' the next succeeding reaction stage of the series.

6. A process of alkylating isobutane by reaction with a normally liquid olefin in the presence of concentrated sulfuric acid in a plurality of reactors through which the sulfuric acid passes in series, fresh sulfuric acid being supplied only to the first of said reactors while used catalyst phase is remove Tom the system only as catalyst withdrawn fro the last of said reactors. which comprises separately feeding fresh isobutane and said olefin to each of said reactors, maintaining an acid concentration of about 92% to 97% in the first of said reactors by feeding fresh sulfuric acid of higher concentration thereto, maintaining a lower acid concentration within the range of about 88% to 95% in the next succeeding reactor by feeding thereto a part of the reacted emulsion withdrawn from the first said reactor prior to any separation thereof and separately separating reacted emuslion from each of said reactors for recovery of isobutane alkylation product therefrom.

7. In a process of alkylating isobutane by reaction with a normally gaseous olefin in the presence of concentrated sulfuric acid, the steps of agitating isobutane, said olefin and sulfuric acid under alkylating conditions, withdrawing a part of the resulting emulsion, separating a portion of the withdrawn emulsion into a hydrocarbon phase and an acid phase, removing the separated hydrocarbon phase from the system, returning the separated acid to said reaction and feeding the remainder of said withdrawn emulsion to a second reaction zone in which it is contacted with isobutane and olefin free from alkylation products.

8. In a process of alkylating an isoparafiin by reaction with an olefin in the presence of an acid alkyation catalyst, the steps of agitating said isoparafifln, olefin and acid alkylation catalyst under alkylating conditions, withdrawing a part of the resulting emulsion, separating a portion of the withdrawn emulsion into a hydrocarbon phase and alkylation catalyst phase, removing the separated hydrocarbon phase from the system, returning the separated alkylation catalyst to said reaction and feeding the remainder of said withdrawn emulsion to a second reaction zone in which it is contacted with isoparafiin and olefin free from alkylation products.

ISAAC M. HEMPHILL. 

